Search

ZnFe 2 O 4 is an n-type semiconductor spinel oxide with promising applications in various fields, including photocatalysis. This study reports the successful synthesis of a novel ZnFe 2 O 4 derivative based on Prussian Blue Analogues (PBAs) through an electrosynthesis method. To enhance photocatalytic performance, the synthesized ZnFe 2 O 4 was employed as a cocatalyst in p-n junction materials, specifically CuO/ZnFe 2 O 4 . Our findings reveal that introducing ZnFe 2 O 4 could significantly improve the photocatalytic activity and hydrogen (H 2 ) production rate of the CuO/ZnFe 2 O 4 system compared to bare CuO. This enhancement was sustained over an extended operational period, indicating the material's potential for long-term use in photocatalytic applications. The superior performance of the ZnFe 2 O 4 cocatalyst is attributed to its efficient charge separation and improved light absorption properties, which collectively contribute to higher photocatalytic efficiency. This study highlights the potential of PBA-based derivative ZnFe 2 O 4 as an effective cocatalyst in developing advanced photocatalytic systems for sustainable hydrogen production., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

One-dimensional (1D) ordered TiO 2 nanotubes exhibit exceptional charge transfer capabilities, making them suitable candidates for constructing visible-light-active photoanodes in selective PEC oxidation reactions. Herein, we employed a facile and easily scalable electrochemical method to fabricate Au-CoO x -deposited ordered TiO 2 nanotubular array photoanodes. The improved visible light absorption capacity of TiO 2 -Au-CoO x , with unhampered 1D channels and the controlled integration of Au between TiO 2 and CoO x , along with their synergistic interaction, have been identified as the most promising strategy for enhanced PEC performance, as evidenced by an IPCE of 3.7% at 450 nm. Furthermore, the robust interfacial charge transfer pathway from CoO x to the TiO 2 surface via the Au mediator promotes the migration of photogenerated electrons and enables the accumulation of holes on the surface of CoO x . These holes are then efficiently utilized by oxidants such as methanol or lignin to generate value-added products, highlighting the potential of this system for advanced PEC applications.

This study presents a novel approach to fabricating anodic Co-F-WO 3 layers via a single-step electrochemical synthesis, utilizing cobalt fluoride as a dopant source in the electrolyte. The proposed in situ doping technique capitalizes on the high electronegativity of fluorine, ensuring the stability of CoF 2 throughout the synthesis process. The nanoporous layer formation, resulting from anodic oxide dissolution in the presence of fluoride ions, is expected to facilitate the effective incorporation of cobalt compounds into the film. The research explores the impact of dopant concentration in the electrolyte, conducting a comprehensive characterization of the resulting materials, including morphology, composition, optical, electrochemical, and photoelectrochemical properties. The successful doping of WO 3 was confirmed by energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), Raman spectroscopy, photoluminescence measurements, X-ray photoelectron spectroscopy (XPS), and Mott-Schottky analysis. Optical studies reveal lower absorption in Co-doped materials, with a slight shift in band gap energies. Photoelectrochemical (PEC) analysis demonstrates improved PEC activity for Co-doped layers, with the observed shift in photocurrent onset potential attributed to both cobalt and fluoride ions catalytic effects. The study includes an in-depth discussion of the observed phenomena and their implications for applications in solar water splitting, emphasizing the potential of the anodic Co-F-WO 3 layers as efficient photoelectrodes. In addition, the research presents a comprehensive exploration of the electrochemical synthesis and characterization of anodic Co-F-WO 3 , emphasizing their photocatalytic properties for the oxygen evolution reaction (OER). It was found that Co-doped WO 3 materials exhibited higher PEC activity, with a maximum 5-fold enhancement compared to pristine materials. Furthermore, the studies demonstrated that these photoanodes can be effectively reused for PEC water-splitting experiments.

Dental implants have become a routine, affordable, and highly reliable technology to replace tooth loss. In this regard, titanium and its alloys are the metals of choice for the manufacture of dental implants because they are chemically inert and biocompatible. However, for special cohorts of patients, there is still a need for improvements, specifically to increase the ability of implants to integrate into the bone and gum tissues and to prevent bacterial infections that can subsequently lead to peri-implantitis and implant failures. Therefore, titanium implants require sophisticated approaches to improve their postoperative healing and long-term stability. Such treatments range from sandblasting to calcium phosphate coating, fluoride application, ultraviolet irradiation, and anodization to increase the bioactivity of the surface. Plasma electrolytic oxidation (PEO) has gained popularity as a method for modifying metal surfaces and delivering the desired mechanical and chemical properties. The outcome of PEO treatment depends on the electrochemical parameters and composition of the bath electrolyte. In this study, we investigated how complexing agents affect the PEO surfaces and found that nitrilotriacetic acid (NTA) can be used to develop efficient PEO protocols. The PEO surfaces generated with NTA in combination with sources of calcium and phosphorus were shown to increase the corrosion resistance of the titanium substrate. They also support cell proliferation and reduce bacterial colonization and, hence, lead to a reduction in failed implants and repeated surgeries. Moreover, NTA is an ecologically favorable chelating agent. These features are necessary for the biomedical industry to be able to contribute to the sustainability of the public healthcare system. Therefore, NTA is proposed to be used as a component of the PEO bath electrolyte to obtain bioactive surface layers with properties desired for next-generation dental implants.

Surface-enhanced Raman spectroscopy (SERS) substrates prepared by immobilizing silver cubic nanoparticles (Ag CNPs) on titanium dioxide nanotubes (TiO 2 NTs) were used for investigations of the "coffee ring" (CR) effect and its impact on spatial reproducibility of measured Raman signals in comparison with flat surfaces (Ti and Si) where the CR effect is usually significant. The immobilization of nanoparticles from drops, which is a very simple technique, usually does not permit a homogeneous distribution of deposited NPs because there is significant accumulation of the material at the boundary of the drying area. Our proposed SERS substrates effectively reduced the CR effect through the use of well-ordered nanostructures where a smaller number of Ag CNPs were transferred to the boundary region. It was not only the surface morphology that was important but also the physicochemical properties of TiO 2 NTs, such as wettability. The wettability of the prepared samples was determined by measuring the static water contact angle (WCA), and the chemical composition near the boundary of the drying area was studied using Auger electron spectroscopy. The morphology of the substrates obtained was characterized using scanning electron microscopy. Our studies showed that reducing the coffee ring effect increased the spatial reproducibility of the measured SERS signal in the area of the deposited CNPs. Therefore, the platforms obtained may be very useful in commercial SERS applications., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

The nitrogen doping of titanium dioxide nanotubes (TiO 2 NTs) was investigated as a result of well-controlled plasma nitriding of TiO 2 NTs at a low temperature. This way of nitrogen doping is proposed as an alternative to chemical/electrochemical methods. The plasma nitriding process was performed in a preparation chamber connected to an X-ray photoelectron spectroscopy (XPS) spectrometer, and the nitrogen-doped TiO 2 NTs were next investigated in situ by XPS in the same ultrahigh vacuum (UHV) system. The collected high-resolution (HR) XPS spectra of N 1s, Ti 2p, O 1s, C 1s, and valence band (VB) revealed the formation of chemical bonds between titanium, nitrogen, and oxygen atoms as substitutional or interstitial species. Moreover, the results provided a characterization of the electronic states of N-TiO 2 NTs generated by various plasma nitriding and annealing treatments. The VB XPS spectrum showed a reduction in the TiO 2 band gap of about 0.6 eV for optimal nitriding and heat-treated conditions. The TiO 2 NTs annealed at 450 or 650 °C in air (ex situ) and nitrided under UHV conditions were used as reference materials to check the formation of Ti-N bonds in the TiO 2 lattice with a well-defined structure (anatase or a mixture of anatase and rutile). Scanning electron microscopy microscopic observations of the received materials were used to evaluate the morphology of the TiO 2 NTs after each step of the nitriding and annealing treatments., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Characterizing materials at small scales presents major challenges in the engineering of nanocomposite materials having a high specific surface area. Here, we show the application of electron tomography to describe the three-dimensional structure of highly ordered TiO 2 nanotube arrays modified with Pt nanoparticles. The titanium oxide nanotubes were prepared by the electrochemical anodization of a Ti substrate after which Pt was deposited by magnetron sputtering. Such a composite shows high electrochemical activity that depends on the amount of the metal and the morphological parameters of the microstructure. However, a TiO 2 structure modified with metallic nanoparticles has never been visualized in 3D, making it very difficult to understand the relationship between electrocatalytic activity and morphology. In this paper, TiO 2 nanotubes of different sizes and different amounts of Pt were analyzed using the electron microscopy technique. Electrocatalytic activity was studied using the cyclic voltammetry (CV) method. For selected samples, electron tomography 3D structure reconstruction was performed to describe their fine microstructure. The highest activity was detected in the sample having bigger nanotubes (25 V) where the porosity of the structure was high and the Pt content was 0.1 mg cm -2 . 3D imaging using electron tomography opens up new possibilities in the design of electrocatalytic materials.

Titanium oxide nanotube layers with silver and zinc nanoparticles are attracting increasing attention in the design of bone and dental implants due to their antimicrobial potential and their ability to control host cell adhesion, growth, and differentiation. However, recent reports indicate that the etiology of dental infections is more complex than has been previously considered. Therefore, the antimicrobial potential of dental implants should be evaluated against at least several different microorganisms cooperating in human mouth colonization. In this study, Ag and Zn nanoparticles incorporated into titanium oxide nanotubular layers were studied with regard to how they affect Candida albicans, Candida parapsilosis, and Streptococcus mutans. Layers of titanium oxide nanotubes with an average diameter of 110 nm were fabricated by electrochemical anodization, annealed at 650 °C, and modified with approx. 5 wt % Ag or Zn nanoparticles. The surfaces were examined with the scanning electron microscopy-energy dispersive X-ray analysis, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy techniques and subjected to evaluation of microbial-killing and microbial adhesion-inhibiting potency. In a 1.5 h long adhesion test, the samples were found more effective toward yeast strains than toward S. mutans. In a release-killing test, the microorganisms were almost completely eliminated by the samples, either within 3 h of contact (for S. mutans) or 24 h of contact (for both yeast strains). Although further improvement is advisable, it seems that Ag and Zn nanoparticles incorporated into TiO 2 nanotubular surfaces provide a powerful tool for reducing the incidence of bone implant infections. Their high bidirectional activity (against both Candida species and S. mutans) makes the layers tested particularly promising for the design of dental implants.

Many phosphorylated nucleoside derivatives have therapeutic potential, but their application is limited by problems with membrane permeability and with intracellular delivery. Here, we prepared polypyrrole microvessel structures modified with superparamagnetic nanoparticles for use as potential carriers of nucleotides. The microvessels were prepared via the photochemical polymerization of the monomer onto the surface of aqueous ferrofluidic droplets. A complementary physicochemical analysis revealed that a fraction of the nanoparticles was embedded in the microvessel walls, while the other nanoparticles were in the core of the vessel. SQUID (superconducting quantum interference device) measurements indicated that the incorporated nanoparticles retained their superparamagnetic properties; thus, the resulting nanoparticle-modified microvessels can be directed by an external magnetic field. As a result of these features, these microvessels may be useful as drug carriers in biomedical applications. To demonstrate the encapsulation of drug molecules, two labeled mRNA cap analogues, nucleotide-derived potential anticancer agents, were used. It was shown that the cap analogues are located in the aqueous core of the microvessels and can be released to the external solution by spontaneous permeation through the polymer walls. Mass spectrometry analysis confirmed that the cap analogues were preserved during encapsulation, storage, and release. This finding provides a foundation for the future development of anticancer therapies and for the delivery of nucleotide-based therapeutics.

This article reports on the fabrication and characterization of plasmonic interfaces composed of a sandwiched structure comprising a tin-doped indium oxide (ITO) substrate, gold nanostructures (Au NSs), and a thin ITO film overcoating. The change in the optical characteristics of the ITO/Au NSs/ITO interfaces as a function of the ITO overlayer thickness (d(ITO) = 0-200 nm) was followed by recording UV-vis transmission spectra. The influence of the thickness of the ITO overcoating on the position and shape of the plasmonic signal is discussed. The possibility to functionalize the ITO/Au NSs/ITO interfaces chemically is demonstrated by covalently linking ethynyl ferrocene to azide-terminated ITO/Au NSs/ITO interfaces. The resulting interfaces were characterized using X-ray photoelectron spectroscopy (XPS), electrochemical (cyclic voltammetry and differential pulse voltammetry) techniques, and UV-vis transmission spectroscopy.

Zinc, silicon, and steel superhydrophobic surfaces were prepared by a simple solution-immersion technique. In the case of zinc, the method consists of dipping of the substrate in a prehydrolyzed methanol solution of 1H,1H,2H,2H-(perfluorooctyl)trichlorosilane [CF(3)(CF(2))(5)(CH(2))(2)SiCl(3), PFTS] for 24 h at 50 degrees C. Micron-sized spheres (1.7-2 microm in diameter) were formed on the zinc substrate at 50 degrees C, while a featureless coating was obtained when the solution-immersion process was conducted at room temperature. When the reaction was performed at room temperature, the formation of superhydrophobic coatings took several days (up to 5 days). In contrast, immersion of silicon or steel substrates in the PFTS/methanol solution led to the formation of hydrophobic interfaces even for a prolonged immersion period at 50 degrees C. The formation of superhydrophobic surfaces on silicon and steel surfaces was only possible if a zinc foil was added in the PFTS/methanol solution containing the silicon or steel substrate. X-ray photoelectron spectroscopy analysis was used to characterize the resulting surfaces and to underline a plausible reaction mechanism.

This paper reports on the preparation of silver/antimony-doped tin oxide (Ag/SnO(2):Sb) hybrid interfaces using magnetron sputtering and their characterization. The influence of the Sn target composition (doping with 2 or 5% Sb) on the electrochemical and electrical characteristics of the hybrid interface was investigated using X-ray photoelectron spectroscopy (XPS), sheet resistance measurements, cyclic voltammetry, scanning tunneling microscopy (STM) and surface plasmon resonance (SPR). The best interface in terms of electrical conductivity and SPR signal is a hybrid interface with a 8.5 +/- 0.3 nm thick SnO(2):Sb layer obtained from a Sn target with 2% Sb deposited on 38 nm thick silver film. Different strategies to link functional groups onto the Ag/SnO(2):Sb interface are also presented.